EP0142785A2 - Trihaloallylthiocyanates, procédé pour leur préparation et leur application conmme microbicide - Google Patents

Trihaloallylthiocyanates, procédé pour leur préparation et leur application conmme microbicide Download PDF

Info

Publication number
EP0142785A2
EP0142785A2 EP84113507A EP84113507A EP0142785A2 EP 0142785 A2 EP0142785 A2 EP 0142785A2 EP 84113507 A EP84113507 A EP 84113507A EP 84113507 A EP84113507 A EP 84113507A EP 0142785 A2 EP0142785 A2 EP 0142785A2
Authority
EP
European Patent Office
Prior art keywords
trihaloallyl
thiocyanates
bromine
iodine
thiocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP84113507A
Other languages
German (de)
English (en)
Other versions
EP0142785B1 (fr
EP0142785A3 (en
Inventor
Hans-Georg Dr. Schmitt
Wilfried Dr. Paulus
Hermann Dr. Genth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AT84113507T priority Critical patent/ATE25970T1/de
Publication of EP0142785A2 publication Critical patent/EP0142785A2/fr
Publication of EP0142785A3 publication Critical patent/EP0142785A3/de
Application granted granted Critical
Publication of EP0142785B1 publication Critical patent/EP0142785B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/02—Thiocyanates
    • C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms

Definitions

  • the invention relates to new trihaloallyl thiocyanates, a process for their preparation and their use in microbicidal compositions.
  • Preferred trihaloallyl thiocyanates according to the invention are, for example, 2,3,3-triiodallyl thiocyanate, 2,3-dibromo-3-iodo-allyl thiocyanate, 2,3,3-tribromo-allyl thiocyanate, 2,3-diiod-3-chloro-allyl thiocyanate, 2,3 -Diiod-3-bromo-allyl thiocyanate.
  • Alkali in the context of the process according to the invention means the metals of the first group of the periodic table according to Mendeleev.
  • Examples include lithium, sodium, potassium, rubidium and cesium, preferably sodium and potassium.
  • a nucleofugic group is understood to mean an atom or an atomic group which, owing to its ability to stabilize negative charges, enables substitution reactions on the saturated carbon atom.
  • Nucleofuge groups are, for example, halogens such as fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, alkylsulfonyloxy groups such as methylsulfonyloxy, ethylene sulfonyloxy and arylsulfonyloxy such as phenylsulfonyloxy, 4-tolylsulfonyloxy.
  • halogens such as fluorine, chlorine, bromine and iodine, preferably chlorine and bromine
  • alkylsulfonyloxy groups such as methylsulfonyloxy, ethylene sulfonyloxy and arylsulfonyloxy such as phenylsulfonyloxy, 4-tolylsulfonyloxy.
  • trihaloallyl derivatives used as starting compounds are known in part from JP Pat. 82, 112,303, C.A. 97, 177 037 (1982) and can be prepared by processes known per se.
  • Trihaloallyl halides can be obtained by halogenation of halopropargyl halides.
  • Trihaloallyl sulfonic acid is obtained by reacting trihaloallyl alcohols with sulfonyl chlorides.
  • Thiocyanates for the process according to the invention are preferably sodium, potassium and ammonium thiocyanate.
  • the process according to the invention can optionally be carried out in the presence of a solvent or diluent.
  • Polar solvents or diluents which do not change under the reaction conditions are generally used as solvents or diluents.
  • solvents or diluents water, alcohols, such as methanol and ethanol, ethers, such as dioxane or tetrahydrofuran, ketones, such as acetone, amides, such as dimethylformamide, and nitriles, such as acetonitrile.
  • the process according to the invention is generally carried out in the temperature range from -20 ° C. to 100 ° C., preferably in the range from 0 ° C. to 60 ° C.
  • the process according to the invention is carried out at normal pressure. However, it can also be carried out with overpressure or underpressure.
  • the components of the process according to the invention are usually used in equimolar amounts.
  • a catalyst such as sodium iodide
  • the method according to the invention can be carried out, for example, as follows.
  • the thiocyanate is optionally dissolved or suspended in a solvent and the trihaloallyl derivative is added. If appropriate in the presence of a catalyst, the reaction mixture is stirred at the desired reaction temperature.
  • the trihaloallyl thiocyanates according to the invention are obtained in a manner known per se by concentration, separation of the salt formed, recrystallization or reprecipitation.
  • the trihaloallyl thiocyanates according to the invention can be used as active ingredients for combating microorganisms, preferably in industrial materials.
  • industrial materials are non-living materials that have been prepared for use in technology.
  • technical materials that are to be protected against microbial change or destruction by the active ingredient according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials that can be decomposed by microorganisms .
  • parts of production systems for example cooling water circuits, which may be affected by microorganisms, may also be mentioned.
  • technical materials are preferably adhesives, glues, paper and cardboard, leather, wood, paints, cooling lubricants and the cooling circuits.
  • the active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules.
  • Organic solvents for the active ingredients can be, for example, alcohols, such as lower aliphatic alcohols, preferably ethanol or isopropanol, or benzyl alcohol, ketones such as acetone or methyl ethyl ketone, liquid hydrocarbons such as gasoline fractions, halogenated hydrocarbons such as 1,2-dichloroethane.
  • alcohols such as lower aliphatic alcohols, preferably ethanol or isopropanol, or benzyl alcohol, ketones such as acetone or methyl ethyl ketone
  • liquid hydrocarbons such as gasoline fractions
  • halogenated hydrocarbons such as 1,2-dichloroethane.
  • microbicidal agents according to the invention generally contain the active ingredient in an amount of 0.5 to 95 parts by weight, preferably 1 to 50% by weight.
  • the application concentration of the active compounds according to the invention depends on the type and the occurrence of the microorganisms to be controlled, and on the composition of the material to be protected.
  • the optimal amount can be determined by test series.
  • the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.01 to 0.5% by weight, based on the material to be protected.
  • the new active substances according to the invention can also be present in a mixture with other known active substances.
  • reaction mixture is concentrated on a rotary evaporator, the residue is stirred into 500 ml of water, the solid precipitate is filtered off with suction and the desiccator is dried.
  • An agar that contains broth as the nutrient medium is mixed with the active substances listed in Table 2 in concentrations of 1 to 5000 mg / l. Then the culture medium is infected with Escherichia coli or Staphylococcus aureus and the infected medium is kept for 2 weeks at 28 ° C and 60 to 70% relative humidity.
  • the MIC is the lowest concentration of active ingredient at which no growth occurs due to the type of microbe used.
  • Substances according to the invention are used in concentrations of 0.1 to 100 mg / 1 in Allen's nutrient solution (Arch. Mikrobiol. 17, 34 to 53 (1952)), which are dissolved in 4 liters of sterile water, 0.2 g of ammonium chloride, and 4.0 g Contains sodium nitrate, 1.0 g dipotassium hydrogen phosphate, 0.2 g calcium chloride, 2.05 g magnesium sulfate, 0.02 g iron chloride and 1% caprolactam, dissolved in a little acetone. Shortly beforehand, the nutrient solution is infected with mucus organisms (approx. 10 6 germs / ml) which have been isolated from spin water circuits used in the production of polyamide.
  • Nutrient solutions that have the minimum inhibitory concentration (MIC) or larger concentrations of active ingredient are still completely clear after 3 weeks of culture at room temperature, ie the noticeable increase in microbes and mucus formation after 3 to 4 days in active ingredient-free nutrient solutions is omitted.
  • MIC minimum inhibitory concentration
  • a mixed culture of green, blue, brown and diatoms (Stichococcus bacillaris Naegeli, Euglena gracilis Klebs, Chlorella pyrenoidosa Chick, Phormidium foveolarum Gomont, Oscillatoria geminata Meneghini and Phaeodactylum tricornutum Bohlin) is bubbled with air from Arch 17, 34 to 53 (1952)), based on 4 liters of sterile water 0.2 g ammonium chloride, 4.0 g sodium nitrate, 1.0 g dipotassium hydrogen phosphate, 0.2 g calcium chloride, 2.05 g magnesium sulfate, 0.02 g contains iron chloride and 1% caprolactam. After 2 weeks the nutrient solution is colored deep green-blue due to intensive algae growth. The death of the algae after the addition of active substances according to the invention can be recognized by the decolorization of the nutrient solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP84113507A 1983-11-17 1984-11-08 Trihaloallylthiocyanates, procédé pour leur préparation et leur application conmme microbicide Expired EP0142785B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84113507T ATE25970T1 (de) 1983-11-17 1984-11-08 Trihaloallylthiocyanate, ein verfahren zu ihrer herstellung und ihre verwendung in mikrobiziden mitteln.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3341556 1983-11-17
DE19833341556 DE3341556A1 (de) 1983-11-17 1983-11-17 Trihaloallylthiocyanate, ein verfahren zu ihrer herstellung und ihre verwendung in mikrobiziden mitteln

Publications (3)

Publication Number Publication Date
EP0142785A2 true EP0142785A2 (fr) 1985-05-29
EP0142785A3 EP0142785A3 (en) 1985-09-11
EP0142785B1 EP0142785B1 (fr) 1987-03-18

Family

ID=6214550

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84113507A Expired EP0142785B1 (fr) 1983-11-17 1984-11-08 Trihaloallylthiocyanates, procédé pour leur préparation et leur application conmme microbicide

Country Status (8)

Country Link
US (1) US4545994A (fr)
EP (1) EP0142785B1 (fr)
JP (1) JPS60116665A (fr)
AT (1) ATE25970T1 (fr)
CA (1) CA1234577A (fr)
DE (2) DE3341556A1 (fr)
DK (1) DK548084A (fr)
ZA (1) ZA848950B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8722358D0 (en) * 1987-09-23 1987-10-28 Ici Plc Compound

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3170942A (en) * 1962-04-12 1965-02-23 Stauffer Chemical Co Chlorinated allyl thiocyanates

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB895186A (en) * 1959-09-01 1962-05-02 Bayer Ag Polyhalogenoethyl-thiocyanates and pesticidal compositions containing them
US3212963A (en) * 1961-10-17 1965-10-19 American Cyanamid Co Trans dithiocyanoethylene and its derivatives as industrial preservatives
US4087451A (en) * 1977-04-20 1978-05-02 Kewanee Industries, Inc. 2,3-Dihalo-1,4-dithiocyano-2-butenes and their homologs

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3170942A (en) * 1962-04-12 1965-02-23 Stauffer Chemical Co Chlorinated allyl thiocyanates

Also Published As

Publication number Publication date
DE3462689D1 (en) 1987-04-23
EP0142785B1 (fr) 1987-03-18
DK548084D0 (da) 1984-11-16
DE3341556A1 (de) 1985-05-30
CA1234577A (fr) 1988-03-29
ZA848950B (en) 1985-07-31
JPS60116665A (ja) 1985-06-24
EP0142785A3 (en) 1985-09-11
US4545994A (en) 1985-10-08
ATE25970T1 (de) 1987-04-15
DK548084A (da) 1985-05-18

Similar Documents

Publication Publication Date Title
EP0199047B1 (fr) Iodopropargyléthers, leur procédé de préparation et leur utilisation
EP0212281B1 (fr) Dérivés de l'hétéroaryl-1 aryl-4 pyrazole
EP0106243B1 (fr) Azolyl-méthylamines, leur préparation et leur utilisation dans des agents microbicides
DD209715A5 (de) Schaedlingsbekaempfungsmittel
EP0142785B1 (fr) Trihaloallylthiocyanates, procédé pour leur préparation et leur application conmme microbicide
EP0146774B1 (fr) Utilisation de 3-amino-1,2 benzisothiazoles comme microbiocides pour protéger des matériaux techniques
EP0045907A1 (fr) Utilisation de N-alkyl-2,3-dichloro-maléinimides comme microbicides
EP0120238B1 (fr) Agent microbiocide pour protéger les matériaux techniques
EP0108352B1 (fr) 3-(3-Iodopropargyl)-benzo-1,2,3-triazin-4-ones, leur procédé de préparation et leur application comme microbicides
EP0071863B1 (fr) Utilisation de N-(dichlorofluorométhylthio)-3,6-endométhylène-delta-4-tétrahydrophtalimide
EP0094539A1 (fr) Halogénopropargylformamides
EP0209819B1 (fr) 3-(3-Iodopropargyloxy)propionitrile, un procédé pour sa préparation et son utilisation
EP0170168B1 (fr) N,N diéthyl, N'aryl N'(dichlorofluorométhylthio) sulfamide-microbiocides
EP0148442B1 (fr) Sulfures halogénés, procédé pour leur préparation et leur emploi dans des compositions microbicides
EP0291800B1 (fr) Iodopropargyléthers de cyanhydrines, un procédé pour leur préparation et leur utilisation comme microbicides
EP0047850B1 (fr) Utilisation de nitroso-4-pyrazoles dans des compositions microbicides
EP0217108B1 (fr) Agent conservateur de matériaux
EP0195238B1 (fr) Indazoles N-sulfénylés fluorés, leur procédé de préparation et leur application
EP0161480B1 (fr) N-iodepropargyl-chlorométhanesulfonamide
DE3920027A1 (de) Dibrompropanol-derivate, verfahren zur herstellung und ihre verwendung
EP0066769A1 (fr) Fungicides pour la protection de matériaux
EP0159644A2 (fr) N-(Dichlorofluorométhylthio)-3,4-diméthylmaléinimide, procédé de préparation et utilisation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19841108

AK Designated contracting states

Designated state(s): AT BE DE FR GB IT NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

RHK1 Main classification (correction)

Ipc: C07C161/00

RHK1 Main classification (correction)

Ipc: C07C161/02

RTI1 Title (correction)
AK Designated contracting states

Designated state(s): AT BE DE FR GB IT NL SE

17Q First examination report despatched

Effective date: 19860121

D17Q First examination report despatched (deleted)
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE FR GB IT NL SE

REF Corresponds to:

Ref document number: 25970

Country of ref document: AT

Date of ref document: 19870415

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3462689

Country of ref document: DE

Date of ref document: 19870423

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19871108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19871130

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
BERE Be: lapsed

Owner name: BAYER A.G.

Effective date: 19871130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19880601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19881109

ITTA It: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19891108

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19900731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19900801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 84113507.2

Effective date: 19890728